Packed Column SFC -- Contents -- Chapter 1 Putting Packed Column Supercritical Fluid Chromatography into Perspective -- 1 Introduction -- What Is Packed Column SFC? -- What is a Supercritical Fluid? -- Do Packed and Capillary SFC Compete with Each Other? -- Are Capillaries Inherently Superior? -- Is There a Need for SFC? -- 2 Chromatographic Attributes or Figures of Merit -- Resolution -- Speed -- Sample Capacity -- Sensitivity -- Classes of Detectors -- Sensitivity of Optical Methods -- Column Impedance -- 3 Comparing Separation Techniques Based on Figures of Merit -- The Speed-Resolution-Sensitivity Triangle -- Spidergrams -- 4 Summary -- 5 References -- Chapter 2 Practical Aspects of SFC Hardware -- 1 Introduction -- 2 Instrumental Overview -- Other Configurations -- 3 Practical Aspects of Fluid Supplies -- Supply Line Characteristics to Avoid -- Padded Tanks -- Pre-mixed Binary Fluids -- Empty? -- Inertness -- Safety -- Gas Quality -- 4 Pumps -- Reciprocating Pumps -- Compressibility Adjustment -- Adiabatic Heating -- Leak Compensation -- Mixing Binary Fluids -- 5 Pressure Control -- Fixed Restrictors -- 6 Injection -- Aqueous Injection - Solvent Polarity -- 7 Detection -- UV Detectors -- Optimizing UV Sensitivity -- GC Detectors -- 8 Columns -- 9 References -- Chapter 3 Physical Chemistry of Mobile Phases Used in Packed Column SFC -- 1 Introduction -- 2 Why SFC? Mobile Phase Considerations -- Diffusion Coefficents -- Viscosity -- 3 What's in a Name? or 'There is NO Such Thing as SFC!!' -- Diffusion Coefficients in Near Critical Fluids -- Viscosity of Near Critical Fluids -- Effect of Physical Parameters on Retention -- Summary -- 4 Solvent Strength -- Solvatochromic Dyes -- 5 Elution Strength -- Effect of Density on Retention -- Modifier Effects Change with Column Polarity -- Relative Effect of Modifiers and Density on Retention.

Solubility -- Ultra-High Pressures -- Does Chromatography occur at 'Infinite Dilution'? -- Explaining Non-linear log k' vs. Modifier Concentration Plots -- Limited Density Range in Binary Fluids -- 6 Phase Behaviour -- What's Wrong with Phase Diagrams? -- Modified Fluid Phase Behaviour -- Phase Behaviour of Methanol/Carbon Dioxide Mixtures -- 7 Conclusions -- 8 References -- Chapter 4 Physical Chemistry of the Stationary Phase -- 1 Introduction -- 2 The Nature of the Packing Materials -- Surface Area -- Phase Ratio -- Active Sites -- 3 Adsorption of Mobile Phase Componentrs -- Adsorbed Carbon Dioxide Acts as a Stationary Phase -- Phase Ratio of an Adsorbed Film -- Volumes Adsorbed -- SFC with Pure Carbon Dioxide is Normal Phase -- Swelling -- Chromatographic Evidence of Adsorbed Carbon Dioxide Acting as Part of the Stationary Phase -- 4 Adsorption from Binary Mixture -- Adsorbed Binary Fluids Sometimes Increase Retention -- 5 Polar Additives -- The Roles of Additives -- 6 Choosing an Additive -- Solutes Can Act as Additives -- Support Deactivation - Polymer Based Columns -- 7 Conclusion -- 8 References -- Chapter 5 The Effect of Instrumental Parameters on Retention, Selectivity, and Efficiency -- 1 Introduction -- 2 Summarizing the Effects of Physical Parameters -- 3 The Effect of Physical Parameters in Controlling Retention of Polar Solutes -- Modifier Concentration-Retention Effects -- Pressure and Retention -- Temperature and Retention -- Mobile Phase Flow and Retention -- 4 The Effect of Physical Parameters on Selectivity between Polar Solutes -- Representing Selectivity Changes -- Modifier Concentration and Selectivity -- Pressure and Selectivity -- Temperature and Selectivity -- Flow Rate and Selectivity -- 5 The Effect of Physical Parameters on Efficiency with Polar Solutes -- Pressure and Efficiency -- Temperature and Efficiency.

Mobile Phase Composition and Efficiency -- Flow Rate and Efficiency -- 6 The Effect of Physical Parameters Using Pure Fluids on Non-polar Solutes -- Pressure Control -- Temperature Control -- 7 References -- Chapter 6 Concepts That Simplify Phase Selection -- 1 Introduction -- 2 'Polarity Windows' Concept Helps Choice of Phases -- SFC Is Always Normal Phase -- Contrary Views -- Active Sites -- Avoiding Unwanted Interactions -- Subtle vs. Gross Separations -- The Most Polar Entities Present Dictate Retention -- Examples of Polarity Windows -- 3 Previous Polarity Scales in GC, LC, and SFC -- The ϵ0 Elution Scale from Normal Phase LC -- Gas Chromatographic Retention -- The 'P' Scale of Solvent Polarity and Selectivity -- Solvatochromic Dyes -- Previous Polarity Scales in SFC -- 4 A Solvent Strength Scale for SFC -- Hydrocarbons, Ethers, Esters, Aldehydes, and Ketones -- Alcohols -- Acids -- Bases -- 5 Factors Affecting Retention -- Functional Group Polarity -- Number of Functional Groups -- Steric Hindrance -- Molecular Size -- Stationary Phase Polarity -- 6 A Summary of Retention in packed Column SFC -- 7 References -- Chapter 7 Systematic Method Development -- 1 Introduction -- 2 Initial Non-chromatographic Tests -- Screening Question No. 1 : Are the Solutes Soluble in a Desirable Mobile Phase? -- Screening Question No. 2: What is the Concentration of the Solute in the Real Sample? -- Screening Question No. 3: Is the Samplew Matrix Compatible with Supercritical Fluids? -- Screening Question No. 4: Is a Universal, Near Constant Response Factor Critical? -- 3 Choosing between Packed and Capillary Columns -- Capillary Columns -- Packed Columns -- 4 Guidelines for Simplifying Method Development -- Solute Characteristics That Affect Retention -- Phase Selection Guidelines -- Instrumental Strategy.

5 Mobile and Stationary Phase Selection Guide for Packed Column SFC -- 6 Step-by-step Speed-Resolution Optimization Scheme for Molecules That Elute with Pure CO2 -- Initial Conditions -- Non-polar Solute, Asymmetric Peaks -- Non-polar Solute, Symmetric Peaks -- 7 Step-by-step Speed-Resolution Optimization Scheme for Molecules That Require Modifier -- Initial Conditions for Polar Solutes -- Observe Peak Shape -- Enhancing Resolution -- 8 Alternative Approaches to Method Development -- Systematic Study of Each Variable -- Additional Approaches to Method Development -- 9 Optimizing the Detection of Real Samples -- Choosing a Detector -- 10 Other Considerations. Injection Volume/Sample Solvent Polarity -- Charpter 8 Pharmaceutical Analysis by Packed Column SFC -- 1 Introduction -- 2 Separations of Some Specific Pharmaceuticals -- Miscellaneous -- Steroids -- Bile Acids -- Ecdysteroids -- Carbohydrates - Oligosaccharides -- Barbiturates -- Opium Alkaloids -- Imidazole Derivatives -- Crotamitron in Creams and Lotions -- Taxol -- Caffine, Theophylline, Theobromine -- Benzodiazepines -- Phenothiazine Anticonvulsants -- Tricyclic Antidepressants -- Stimulants -- Sulfonamides -- Diuretics -- 3 References -- Chapter 9 Chiral Analysis of Drugs -- 1 Introduction -- 2 Characteristics of Chiral Separations -- 3 Developing a Chiral Method -- The Effect of Physical Parameters on Chiral Separations -- Initial Conditions -- Optimization after the Initial Experiment -- Other Figures of Merit of Chiral Analysis -- 4 Some Examples -- Isolation and Detection of Ibuprofen from a Biological Fluid -- Mixed 'Universal' Phase? -- Benzadiazepans and Metabolities -- Long Column as Easiest Way to Increase Resolution -- LC Worked, SFC Didn't -- Other Chiral Separations -- 5 References -- Chapter 10 Separation of Agricultural Chemicals by Packed Column SFC -- 1 Introduction.

2 Trace Contaminants/Quality Control -- 3 Residue Analysis -- Carbamate Pesticides -- Phenylurea Herbicides -- Sulfonylureas -- Triazines -- 4 Screening Methods for Multiple Pesticide Residues -- Programming Selectivity and Retention -- Multiple Detectors -- 5 Summary -- 6 References -- Chapter 11 SFC and the Petroleum Industry -- 1 Group Separations -- Why SFC? -- Other Aspects -- Historical Development -- 2 High Temperature GC vs. SFC -- 3 High Efficiency Packed Column SFC -- 4 Several Instrumental Concerns Seldom Mentioned in Print -- Characteristics of the FID -- The Problem of Changing Split Ratio with Pressure Programming -- 5 References -- Chapter 12 Miscellaneous Applications of Packed Column SFC -- 1 Introduction -- 2 Specific Separations -- Polystyrenes -- Silicone Oils -- Methyl Vinyl Silicone Stationary Phases - Peroxide Reaction Mixtures -- Methyl Methacrylates -- Epoxy Resins -- Polymer Additives -- High Speed Chromatograms -- Triton X-100 -- Natural Products -- Ubiquinones in Legionella -- Underivatized Fatty Acids -- 3 References -- Subject Index.